Anthraquinonyl Schiff base derivative as well as preparation method and application thereof
By developing anthraquinone-based Schiff base derivatives as fluorescence and colorimetric probes, the existing Co2+ and crystal violet detection methods are solved, and the rapid, sensitive and selective detection effect is achieved. It is suitable for Solution and test strip sensor applications.
Patent Information
- Application Number
- CN202411360525.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-27
- Publication Date
- 2025-01-03
AI Technical Summary
The existing Co2+ and crystal violet detection methods have problems such as cumbersome detection process, complex large-scale instruments, cumbersome operation and high cost, especially the detection sensitivity and selectivity of biological samples.
Anthraquinone-based Schiff base derivative was developed as a fluorescent probe and colorimetric probe, which can detect Co2+ and crystal violet in solution, and make a portable sensor to achieve qualitative and quantitative through color change and fluorescence intensity analysis. Test.
Fast, sensitive, and highly selective Co2+ and crystal violet detection are achieved, with portability and low cost, and can identify Co2+ in solution and on test strips, and accurately analyze under different pH conditions.
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Figure CN119241392A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of detection technology, and specifically relates to an anthraquinone-based Schiff base derivative and a preparation method and application thereof. Background Art
[0002] Cobalt (Co) is an essential trace element in the human body and a common component of vitamin B12 (cobalamin) and other biological compounds. 2+ When the concentration is too high, it may seriously affect the health of the body and cause a series of problems such as hypotension, cardiomyopathy and gene mutation. 2+ It will inhibit the metabolism and growth of microorganisms. Excessive Co in the soil 2+ It will be absorbed by crops and then absorbed by the human body through the food chain. Therefore, Co 2+ Sensors are becoming increasingly important in environmental and clinical chemistry. Crystal violet (CV, hereinafter referred to as CV) is widely used in aquaculture because of its good antiseptic and antibacterial properties. However, CV has hidden dangers such as carcinogenicity, teratogenicity, and mutagenicity to organisms. At the same time, CV is easily absorbed by fish tissue and converted into toxic leuco crystal violet (LCV). Therefore, many countries strictly prohibit the use of CV in aquaculture. Based on the threat of CV to aquatic animals and human health, high-sensitivity and high-selectivity detection of CV in biological samples is of great significance.
[0003] Many analytical techniques used in the past, such as voltammetry, ion selective electrodes, atomic absorption spectroscopy, etc., have been used to detect Co 2+ The fluorescence method has attracted wide attention from researchers due to its advantages such as high sensitivity, simple operation, real-time detection and portability. Anthraquinone-based Schiff bases have excellent chromophores and recognition groups, simple synthesis technology, easy modification and good coordination ability. They can be used as fluorescent probes to detect and identify metal ions. The rich color changes of quinone derivatives also provide a good basis for the naked eye to detect metal ions.
[0004] So far, methods such as HPLC, QuEChERS-HPLC, MSPE, and LC-Ms have been used to analyze CV. However, these methods have disadvantages such as long measurement time, use of complex large instruments, and cumbersome operation. Fluorescence methods have attracted much attention due to their advantages such as high sensitivity, simple operation, real-time detection, and portability. Although some fluorescent probes for detecting CV have been reported, most of these probes are synthesized using precious metals and are extremely expensive. There are also few reports on the application of organic molecules in the detection of CV. Summary of the invention
[0005] In order to solve the above problems, the present invention discloses a method which can be applied to Co 2+ Anthraquinone-based Schiff base derivatives for detecting Co and crystal violet and preparation methods thereof; as probes, they can detect Co in solution by colorimetry 2+ , and can also be made into a test paper type portable sensor for naked eye recognition of Co 2+ , can also be applied to fluorescence detection of CV.
[0006] To achieve the above object, the technical solution of the present invention is as follows:
[0007] The present invention provides an anthraquinone-based Schiff base derivative, wherein the chemical formula of the anthraquinone-based Schiff base derivative is C 32 H 28-2n N4O4R 2n (n=1-4), the structure of the anthraquinone-based Schiff base derivative is shown in formula (1):
[0008]
[0009] Wherein, R is H, a heteroatom-containing substituent, a C1-C40 alkyl group, a C2-C40 alkenyl group, a C2-C40 alkynyl group, a C6-C48 aryl group, or a C5-C48 heteroaryl group.
[0010] The present invention also provides a method for preparing anthraquinone-based Schiff base derivative, comprising the following steps:
[0011] (1) mixing 1,4-dihydroxyanthraquinone and sodium dithionite, adding the mixture into a mixed solvent of dioxane and water, and reacting to obtain 2,3-dihydro-9,10-dihydroxy-1,4-anthracenedione;
[0012] (2) dispersing 2,3-dihydro-9,10-dihydroxy-1,4-anthracene dione in a mixed solution of ethylenediamine and methanol to react to obtain 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione;
[0013] (3) dispersing 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione and salicylaldehyde and its derivatives in ethanol to react to obtain an anthraquinone-based Schiff base derivative;
[0014] The anthraquinone-based Schiff base derivative is as shown in claim 1, and the structure of salicylaldehyde and its derivatives is as shown in formula (2):
[0015]
[0016] Wherein, R is H, a heteroatom-containing substituent, a C1-C40 alkyl group, a C2-C40 alkenyl group, a C2-C40 alkynyl group, a C6-C48 aryl group, or a C5-C48 heteroaryl group.
[0017] Furthermore, in step S01, the molar ratio of 1,4-dihydroxyanthraquinone to sodium dithionite is 1:2-5, and the volume ratio of dioxane to water is 1:0.8-1.2.
[0018] Furthermore, in step S01, the reaction temperature is 20-30°C, and the reaction time is 3-6h.
[0019] Furthermore, in step S02, the molar ratio of 2,3-dihydro-9,10-dihydroxy-1,4-anthracene dione to ethylenediamine is 1:40-50, and the volume ratio of ethylenediamine to methanol is 1:1-1.5.
[0020] Furthermore, in step S02, the reaction conditions are: first react at 50-60°C under an inert gas atmosphere for 1-1.5 hours, then remove the inert gas atmosphere, introduce air, continue to react at 50-60°C for 1-1.5 hours, and then react at room temperature for 2-3 hours.
[0021] Furthermore, in step S03, the molar ratio of 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione, salicylaldehyde and its derivatives is 1:2-2.05; the molar volume ratio of 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione and ethanol is 1:15-40 mmol / mL; the reaction temperature is 70-75°C, and the reaction time is 0.5-1 hour.
[0022] The present invention also provides the anthraquinone-based Schiff base derivative as or in the preparation of Co 2+ Applications in colorimetric probes, fluorescent probes and crystal violet fluorescent probes.
[0023] The present invention also provides a Co 2+ The detection sensor comprises the anthraquinone-based Schiff base derivative and a substrate; the anthraquinone-based Schiff base derivative is adsorbed on the substrate. The substrate is a conventional product, such as filter paper, etc.; the specific adsorption operation (method) is a conventional technology.
[0024] The present invention also provides a method for detecting Co in liquid 2+ The method comprises the following specific steps: preparing the anthraquinone-based Schiff base derivative into a 100 ppm standard solution, taking an appropriate amount and mixing it with the detection liquid, adjusting the pH to 10 (alkaline), and detecting the Co in the liquid according to the color change of the sensor. 2+ Qualitative analysis of Co in liquid was performed based on the absorbance at 500 nm. 2+ Qualitative and quantitative analysis of Co in liquid based on the fluorescence intensity at 670-720nm 2+ Qualitative and quantitative analysis; or drop the test liquid onto the test paper containing the anthraquinone-based Schiff base derivative according to claim 1, and perform Co in the liquid according to the color change of the sensor.2+ Qualitative analysis of .
[0025] The present invention also provides a method for detecting CV in a liquid, and the specific steps are as follows: the anthraquinone-based Schiff base derivative is prepared into a 100 ppm standard solution, the pH is adjusted to 5 (acidic), an appropriate amount is taken and mixed with the detection liquid, and the qualitative and quantitative analysis of crystal violet in the liquid is performed according to the fluorescence intensity at 670-720 nm.
[0026] The beneficial effects of the present invention are:
[0027] (1) It can realize Co in solution 2+ and CV detection;
[0028] (2) Realize multi-channel detection Co 2+ (Co can be detected by naked eye in solution 2+ , and Co can be realized in solution 2+ Ultraviolet and fluorescence qualitative and quantitative analysis, and can also be made into portable sensors to identify Co 2+ );
[0029] (3) Rapid response, the detection process has good selectivity, sensitivity and anti-interference ability. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 is a synthetic route diagram of the anthraquinone-based Schiff base derivatives of the present invention;
[0031] Figure 2 An anthraquinone-based Schiff base derivative (A1) of the present invention 1 HNMR spectra;
[0032] Figure 3 An anthraquinone-based Schiff base derivative (A1) of the present invention 13 C NMR spectra;
[0033] Figure 4 The photos and UV-visible absorption spectra of A1 before and after adding different metal ions;
[0034] Figure 5 For the coexisting metal ion pair A1-Co 2+ The influence of absorbance at 500 nm;
[0035] Figure 6 1-17 μM Co 2+ UV-visible absorption spectra of A1 at different concentrations (A) and 0-10 μM Co 2+ Linear change graph of absorbance at 500 nm (B);
[0036] Figure 7To use A1 test paper to indicate Co 2+ photos;
[0037] Figure 8 Containing different concentrations of Co 2+ Fluorescence emission spectrum of A1 solution (A) and the fluorescence intensity at 678 nm and Co 2+ Relationship of concentration (B);
[0038] Fig. 9 The responses of A1 to inorganic interfering ions and CV at 678 nm (A), to organic interfering ions and CV (B), and to CV analogs and CV (C);
[0039] Fig.10 Figure 2 shows the fluorescence emission spectra of A1 solutions containing different concentrations of CV (A) and the relationship between the fluorescence intensity at 678 nm and the CV concentration (B). DETAILED DESCRIPTION
[0040] The present invention will be further explained below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the following specific embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.
[0041] See also Figure 1 The present invention designs and synthesizes a method that can be applied to Co 2+ The anthraquinone-based Schiff base derivative detected by crystal violet is synthesized as follows:
[0042] (1) Synthesis of 2,3-dihydro-9,10-dihydroxy-1,4-anthracene dione: 1,4-dihydroxyanthraquinone (1.2 g, 5.0 mmol) and sodium dithionite (2.61 g, 15.0 mmol) were mixed, 30 ml of dioxane and 30 ml of water were added, and the reaction mixture was allowed to react at room temperature (20-30° C.) for 3 hours, and then the reaction mixture was dried by rotary evaporation. Dichloromethane was added to redissolve the mixture, and the mixture was filtered. The filtrate was dried by rotary evaporation to obtain an orange solid (1.15 g, 95%).
[0043] (2) Synthesis of 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione: 2,3-dihydro-9,10-dihydroxy-1,4-anthracene dione (5 g, 21 mmol) was dispersed in a mixed solution of 50 ml of ethylenediamine and 50 ml of methanol, and reacted at 60°C for 1 hour under an inert gas atmosphere. The inert gas atmosphere was then removed, and air was introduced. The reaction was continued at 50°C for 1 hour and then at room temperature for 2 hours. 50 ml of acetonitrile was added, and a blue solid was obtained by filtration. The solid was washed with ether and dried to obtain 5.61 g of the product (83.9%).
[0044] (3) 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione and salicylaldehyde and its derivatives are dispersed in ethanol at a molar ratio of 1:(2-2.05), reacted at 75°C for 0.5-1 hour, then cooled to room temperature, filtered, washed twice with ethanol and then twice with ether, and dried to obtain the product with a yield of 90%-96%.
[0045] Example 1
[0046] 1,4-dihydroxyanthraquinone (10.0 g, 41.7 mmol) and sodium dithionite (21.75 g, 125.1 mmol) were mixed, 250 ml of dioxane and 250 ml of water were added, and the reaction mixture was dried after 3 hours at room temperature (25°C), and dichloromethane was added to redissolve the mixture and filtered. The filtrate was dried to obtain 2,3-dihydro-9,10-dihydroxy-1,4-anthracenedione (9.48 g, 94%).
[0047] Disperse 2,3-dihydro-9,10-dihydroxy-1,4-anthracene dione (10 g, 42 mmol) in a mixed solution of 100 ml ethylenediamine and 100 ml methanol, react at 60°C for 1.5 hours under an inert gas atmosphere, remove the inert gas atmosphere, introduce air, continue to react at 50°C for 1.5 hours, then turn to room temperature for 2 hours. Add 100 ml acetonitrile, filter to obtain a blue solid, wash with ether and dry to obtain 10.97 g 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione (82%);
[0048] Disperse 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione (0.5 g, 1.54 mmol) and salicylaldehyde (0.376 g, 3.08 mmol) in 25 ml of ethanol, react at 75°C for 0.5 hours, then cool to room temperature, filter, wash twice with ethanol and then twice with ether, and dry to obtain product A1 (0.739 g, 90%). Figure 2 , 1H NMR (400MHz, DMSO-d6, δ / ppm): 13.20 (s, 2H, OH), 10.88 (d, J = 5.3Hz, 2H, NH), 8.59 (s, 2H,CH),8.18(ddd,J=5.3,3.2,1.5Hz,2H,ArH),7.77(ddd,J=5.5,3.4,1.5Hz,2H,ArH ),7.58(d,J=1.6Hz,2H,ArH),7.41(d,J=8.0Hz,2H,ArH),7.32(t,J=7.8Hz,2H,ArH), 6.87(t,J=6.9Hz,4H,ArH),3.89(d,J=5.7Hz,4H,CH2),3.82(d,J=6.0Hz,4H,CH2); refer to Figure 3 , 13 C NMR(101MHz,DMSO-d6)δ180.96,167.33,160.43,145.95,133.76,132.44,131.7 5,125.75,124.69,118.68,118.64,116.46,108.70,58.28,42.84; MS(ESI): m / z 533.2[M+H] + ,555.2[M+Na] + ;
[0049] Example 2
[0050] Disperse 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione (3.24 g, 10 mmol) and 2-hydroxy-1-naphthaldehyde (3.46 g, 20 mmol) in 250 ml of ethanol, react at 75°C for 1 hour, then cool to room temperature, filter, wash twice with ethanol and then twice with ether, and dry to obtain product A2 (5.82 g, 92%). 1H NMR (400MHz, DMSO-d6, δ / ppm): 13.90 (s, 2H, OH), 10.87 (t, J = 6.0Hz, 2H, NH), 9.03 (d, J = 9.6Hz, 2H, CH) ,8.09(dd,J=5.9,3.3Hz,2H,ArH),7.93(d,J=8.5Hz,2H,ArH),7.73(dd,J=5.9,3.3Hz,2H,ArH),7.68( d,J=9.4Hz,2H,ArH),7.60(s,2H,ArH),7.55(d,J=7.8Hz,2H,ArH),7.24(t,J=7.2Hz,2H,ArH),7.09(t ,J=7.4Hz,2H,ArH),6.70(d,J=9.3Hz,2H,ArH),3.91(d,J=5.9Hz,4H,CH2),3.84(t,J=5.9Hz,4H,CH2); 13 C NMR(101MHz,DMSO-d6)δ181.17,176.61,159.89,145.98,137.12,134.17,133.69,132.38,128.78,1 27.69,125.69,125.27,125.14,124.68,122.20,118.53,108.95,106.06,51.10,42.72; MS(ESI): m / z 633.3[M+H] + ;
[0051] Example 3
[0052] 1,4-Bis((2-aminoethyl)amino)anthracene-9,10-dione (0.324 g, 1 mmol) and 3,5-di-tert-butylsalicylaldehyde (0.478 g, 2.04 mmol) were dispersed in 40 ml of ethanol, reacted at 75°C for 0.5 hour, then cooled to room temperature, filtered, washed 3 times with methanol, and dried to obtain product A3 (0.68 g, 90%). 1H NMR (400MHz, DMSO-d6, δ / ppm): 13.82 (s, 2H, OH), 10.87 (t, J = 5.7Hz, 2H, NH), 8. 56(s,2H,CH),8.17(dd,J=5.9,3.3Hz,2H,ArH),7.76(dt,J=5.9,3.5Hz,2H,ArH ),7.55(s,2H,ArH),7.28(d,J=2.4Hz,2H,ArH),7.20(d,J=2.4Hz,2H,ArH),3.8 6(t,J=6.0Hz,4H,CH2),3.81(m,4H,CH2),1.36(s,18H,CH3),1.21(s,18H,CH3); 13 C NMR(101MHz,DMSO-d6)δ182.62,168.02,158.02,145.96,140.25,136.67,134.42,132.16,127.27 ,126.25,126.11,123.42,117.85,110.26,59.43,43.46,35.12,34.20,31.57,29.54; MS(ESI): m / z 757.5[M+H] + ;
[0053] Example 4
[0054] 1,4-Bis((2-aminoethyl)amino)anthracene-9,10-dione (0.324 g, 1 mmol) and 2,5-dihydroxysalicylaldehyde (0.276 g, 2 mmol) were dispersed in 30 ml of ethanol, reacted at 75°C for 0.5 hour, then cooled to room temperature, filtered, washed twice with ethanol and then twice with ether, and dried to obtain product A4 (0.52 g, 92%). 1 H NMR (400MHz, DMSO-d6, δ / ppm): 12.33 (bs, 2H, OH), 10.85 (t, J = 5.7Hz, 2H, NH), 8.95 (b s,2H,OH),8.51(s,2H,CH),8.16(dd,J=5.9,3.3Hz,2H,ArH),7.75(dd,J=5.9,3.3Hz, 2H,ArH),7.51(s,2H,ArH),6.82(d,J=2.9Hz,2H,ArH),6.77(dd,J=8.7,2.9Hz,2H,Ar H),6.71(d,J=8.7Hz,2H,ArH),3.86(t,J=5.7Hz,4H,CH2),3.76(q,J=5.8Hz,4H,CH2); 13C NMR(101MHz,DMSO-d6)δ180.93,167.05,153.00,149.42,145.78,133.76,132.29,1 25.74,124.37,120.07,118.69,116.96,116.63,108.69,58.46,42.97; MS(ESI): m / z 587.2[M+Na] + ;
[0055] The anthraquinone-based Schiff base derivative A1 prepared in Example 1 was dissolved in DMF to prepare a 100 ppm probe solution, and NaCl, Pb(NO3)2, AgNO3, Cd(NO3)2, Fe2(NO3)3, KCl, Cr(NO3)2, Zn(NO3)2, Ba(oAC)2, Co(NO3)2, Ni(NO3)2, Cu(NO3)2, CaCl2, MnCl2, Na2CO3, K3PO4, KF, KBr, K2C2O4, K2SO4, NaNO3, glycine (Gly), L-serine (L-ser), L-cysteine (L-cys), L-alanine (L-ala), L-tryptophan (L-try), thymus Pyrimidine (T), ampicillin (AMP), clarithromycin (CLR), gatifloxacin (GAT), sulfadiazine (SD), sulfathiazole (ST), tetracycline (TE), oxytetracycline (OTC), norfloxacin (NFX), crystal violet (CV), latent crystal violet (LCV), malachite green (MG), and latent malachite green (LMG) were prepared into solutions with a concentration of 600ppm; 3.735mL of DMF was added to a vial, and then 265μLA1 probe solution was added, 0.5ml of distilled water was added first, and then the above-mentioned test solution was added, and the pH was adjusted to 5 (acidic) or 10 (alkaline) with 0.1M HCl solution and 0.1M NaOH solution, and the total volume of the added aqueous solution was 0.8ml. After sufficient reaction, the mixed solution was tested.
[0056] 3 mL of the above alkaline mixed solution (DMF / H2O=5 / 1, v / v) was added to the cuvette, where the A1 solution was 10 μM and the metal ion solution was also 10 μM, and the change of its absorbance with wavelength was recorded. Figure 4 It can be seen that the probe is effective for Co 2+ High selectivity and can achieve Co 2+ of naked eye inspection.
[0057] 3 mL of the above alkaline mixed solution (DMF / H2O=5 / 1, v / v) was added to the cuvette, where the A1 solution was 10 μM and the metal ion solution was also 10 μM, and the change of its absorbance with wavelength was recorded. Figure 5 It can be seen that when the concentration of other metal ions does not exceed Co 2+ When the probe is 2+ The recognition has good anti-interference ability and will not interfere with Co 2+ of naked eye inspection.
[0058] 3 mL of the above alkaline mixed solution (DMF / H2O=5 / 1, v / v) was added to the cuvette, wherein the A1 solution was 10 μM, the Co 2+ The concentration of Figure 6 The experimental results show that as Co 2+ The absorbance of the probe solution at 500 nm gradually increased. 2+ When the concentration reaches the same as that of the probe, i.e. 10 μmol / L, the absorbance no longer increases and the titration reaches saturation. It can be inferred that the probe is 2+ The coordination ratio of the formed complex is 1:1. And in the concentration range of 0-10μM, the absorbance at 500nm is similar to that of Co 2+ The concentration showed a good linear relationship, the linear equation was y = 0.0171x + 0.0142, and the correlation coefficient R 2 was 0.99, and the detection limit was 48.6 nM.
[0059] 2 mL of the above alkaline mixed solution (DMF / H2O=5 / 1, v / v) was added to the cuvette, wherein the A1 solution was 10 μM; Co 2+ The concentration of the fluorescein was gradually increased, and the change of its fluorescence intensity with wavelength was recorded (excitation wavelength: 595nm, emission wavelength: 670-720nm). Figure 8 The experimental results show that as Co 2+ The fluorescence intensity of the probe solution at 670-720nm gradually decreased. 2+ When the probe concentration reaches half, i.e. 5 μmol / L, the fluorescence is almost completely quenched, and the effect of increasing the concentration on the probe fluorescence intensity will be greatly reduced. In the concentration range of 0.1-1 μM, the fluorescence intensity at 678 nm is similar to that of Co 2+ The concentration showed a good linear relationship, the linear equation was y = 0.48x + 0.98, and the correlation coefficient R 2 was 0.99, and the detection limit was 13.1 nM.
[0060] 2 mL of the above acidic mixed solution (DMF / H2O=5 / 1, v / v) was added to the cuvette, wherein the A1 solution was 10 μM and the other analytes were 15 μM, and the changes in their fluorescence intensity at 678 nm were recorded. Fig. 9It can be seen that the probe has high selectivity for CV in aqueous solution, and when the concentration of other analytes does not exceed CV, the probe has good anti-interference in identifying CV in aqueous solution.
[0061] 2 mL of the above acidic mixture was added to the cuvette, in which the A1 solution was 10 μM, the concentration of CV was gradually increased, and the change of its fluorescence intensity with wavelength was recorded (excitation wavelength: 595 nm, emission wavelength: 670-720 nm). Fig.10 The experimental results show that as the CV increases, the fluorescence intensity of the probe solution at 670-720nm also decreases. When the CV concentration reaches 3 times the probe concentration, that is, 30μmol / L, the fluorescence is almost completely quenched. The effect of increasing the concentration on the probe fluorescence intensity will be greatly reduced. In the concentration range of 0.1-10μM, the fluorescence intensity at 678nm is similar to that of Co 2+ The concentration showed a good linear relationship, the linear equation was y = 0.195x + 0.919, and the correlation coefficient R 2 was 0.99, and the detection limit was 23.7 nM.
[0062] The preparation method of A1 test paper is as follows: A1 is dissolved in DMF solution to prepare a 500μM standard solution. Conventional filter paper is cut into a 0.4cm long and 0.3cm wide paper, and 20μL of 500μM standard solution is dripped on the paper to make the solution evenly dispersed on the paper. After drying at room temperature (20-30℃) for one day, the A1 test paper that can be used for detection is obtained.
[0063] A1 test strip as a portable sensor to indicate Co 2+ : First add 40μL DMF solution to the A1 test paper, then add 10μL 1mM aqueous solution of the metal ion to be tested. Under natural light, the color of the test paper can be observed to change quickly. After the test paper is dry, take a photo and the result is as follows: Figure 7 shown.
[0064] Example 5
[0065] Water samples from the laboratory tap, Caiyue Lake, Yueliang Bay and the fish pond in front of the library were taken as samples for testing. The samples were filtered to remove suspended particles, and then the pH was adjusted to neutral with 0.1M hydrochloric acid solution to prevent the precipitation of cobalt ions when cobalt ions were added later. 3.735mL of DMF was added to the vial, and then 265μL of probe A1 solution was added. After adding 0.5ml of the above water sample, the pH was adjusted to 10 (alkaline) with 0.1M HCl solution and 0.1M NaOH solution. The total volume of the added aqueous solution was 0.8ml. After sufficient reaction, the absorbance of the mixed solution at 500nm was tested, and no increase was found, indicating that there was no Co in these water samples. 2+As shown in Table 1, then take Co 2+ The standard solution was added to the treated water sample to prepare solutions of different concentrations. The detected Co 2+ The concentration is close to the added concentration, the recovery rate is between 98% and 109%, and the relative standard deviation is small. Therefore, the anthraquinone-based Schiff base derivative probe A1 prepared by the present invention can be used for the detection of Co in water. 2+ Detection.
[0066] Table 1 Practicality test of Co2+ in actual water samples
[0067]
[0068] Example 6
[0069] The fish samples were purchased from a local supermarket (Nanjing). The fish tissue sample processing process was as follows: First, the fish meat was minced, 10.0 g was weighed and added to 30 mL of CH3CN, and ultrasonicated at room temperature (20-30°C) for 1 h. After centrifugation, the supernatant was collected and filtered, and the filtrate was dried over anhydrous Na2SO4. Subsequently, CH3CN was removed by rotary evaporator at 50°C. The final sample was dissolved in distilled water and placed in a 4°C refrigerator for later use. 3.735 mL of DMF was added to the vial, and then 265 μL of probe A1 solution was added. After adding 100 μL of the above water sample, the pH was adjusted to 5 (acidic) with 0.1 M HCl solution and 0.1 M NaOH solution. The total volume of the added aqueous solution was 0.8 ml. After sufficient reaction, the fluorescence intensity of the mixed solution was tested at 670-720 nm, and it was found that there was almost no change, indicating that there was no CV in the fish tissue fluid. Then, the CV standard solution was added to the treated water sample to prepare solutions of different concentrations, as shown in Table 2. The detected CV concentration was close to the added concentration, the recovery rate was between 97% and 104%, and the relative standard deviation was small. Therefore, the anthraquinone-based Schiff base derivative probe A1 prepared by the present invention can be used for the detection of CV in water.
[0070] Table 2 Practicality test of CV in actual fish tissue
[0071]
[0072] It should be noted that the above content only illustrates the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. For ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications all fall within the protection scope of the claims of the present invention.
Claims
1. An anthraquinone-based Schiff base derivative, characterized in that: The chemical formula of the anthraquinone-based Schiff base derivative is C 32 H 28-2n N4O4R 2n (n=1-4), the structure of the anthraquinone-based Schiff base derivative is shown in formula (1): Wherein, R is H, a heteroatom-containing substituent, a C1-C40 alkyl group, a C2-C40 alkenyl group, a C2-C40 alkynyl group, a C6-C48 aryl group, or a C5-C48 heteroaryl group.
2. A method for preparing anthraquinone-based Schiff base derivative, characterized in that: The following steps are involved: (1) mixing 1,4-dihydroxyanthraquinone and sodium dithionite, adding the mixture into a mixed solvent of dioxane and water, and reacting to obtain 2,3-dihydro-9,10-dihydroxy-1,4-anthracenedione; (2) dispersing 2,3-dihydro-9,10-dihydroxy-1,4-anthracene dione in a mixed solution of ethylenediamine and methanol to react to obtain 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione; (3) dispersing 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione and salicylaldehyde and its derivatives in ethanol to react to obtain an anthraquinone-based Schiff base derivative; The anthraquinone-based Schiff base derivative is as shown in claim 1, and the structure of salicylaldehyde and its derivatives is as shown in formula (2): Wherein, R is H, a heteroatom-containing substituent, a C1-C40 alkyl group, a C2-C40 alkenyl group, a C2-C40 alkynyl group, a C6-C48 aryl group, or a C5-C48 heteroaryl group.
3. The method for preparing an anthraquinone-based Schiff base derivative according to claim 2, characterized in that: In step S01, the molar ratio of 1,4-dihydroxyanthraquinone to sodium dithionite is 1:2-5, and the volume ratio of dioxane to water is 1:0.8-1.
2.
4. The method for preparing an anthraquinone-based Schiff base derivative according to claim 2, characterized in that: In step S01, the reaction temperature is 20-30°C, and the reaction time is 3-6h.
5. The method for preparing an anthraquinone-based Schiff base derivative according to claim 2, characterized in that: In step S02, the molar ratio of 2,3-dihydro-9,10-dihydroxy-1,4-anthracene dione to ethylenediamine is 1:40-50, and the volume ratio of ethylenediamine to methanol is 1: (1-1.5)。 6. The method for preparing an anthraquinone-based Schiff base derivative according to claim 2, characterized in that: In step S02, the reaction conditions are: first react at 50-60° C. under an inert gas atmosphere for 1-1.5 h, then remove the inert gas atmosphere, introduce air, continue to react at 50-60° C. for 1-1.5 h, and then react at room temperature for 2-3 h.
7. The method for preparing an anthraquinone-based Schiff base derivative according to claim 2, characterized in that: In step S03, the molar ratio of 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione, salicylaldehyde and its derivatives is 1:2-2.05; the molar volume ratio of 1,4-bis((2-aminoethyl)amino)anthracene-9,10-dione and ethanol is 1:15-40mmol / mL; the reaction temperature is 70-75°C, and the reaction time is 0.5-1 hour.
8. An anthraquinone-based Schiff base derivative prepared by the preparation method according to claim 2-8 for the determination of crystal violet or Co 2+ Application of optical properties.
9. An anthraquinone-based Schiff base derivative prepared by the preparation method according to claim 2-8 is used in the preparation of Co 2+ Colorimetric probe, Co 2+ Application of fluorescent probes and crystal violet fluorescent probes.